Germicidal detergent compositions containing amides and halogenated amides of sulfur-containing phenol carboxylic acids



rates 3,311,562 GERMECKDAL DETERGENT COMPOSITIONS (IGN- TAINING AMHDES AND HALOGENATED AM- HDES F SULFUR-C(BNTAWING PHENQL CAR- BQXYLTC ACEDS Herbert C. Stacker, Ho-Ho-Kus, NJ. 07423 No Drawing. Fiied Feb. 17, 1964, Ser. No. 345,063 6 (Ilaims. (Cl. 252106) ilnite wherein R is an aromatic radical selected from the class consisting of phenyl and naphthyl groups, A is an atom selected from the class of oxygen and sulfur, X is a halogen atom selected from the class consisting of fluorine, chlorine, bromine and iodine, a is a numeral from 0 and 2, and b is a numeral from 0 and 3.

Condensation products of carboxylic acids with ar0- matic amines have been known to possess some dyeing characteristics, but none of the compounds have been considered to have suflicient germicidal potency to justify commercial consideration.

It has been discovered that the amide condensation products of the lower aromatic phenols and thiophenols, with the lower aromatic amines and halogenated amines, show exceptionally high germicidal potency. The aromatic group may be phenyl or naphthyl, and both the phenol and amine groups may contain halogen substitutions,

The germicidal compounds of the present invention may be prepared in accordance with the method outlined by Hopper, MacGregor and Wilson, in the January 1941 issue of the Journal of the Society of Dyers and Colourists, page 6. Table I lists a number of compounds prepared in accordance with the present invention, and gives their germicidal effectiveness against S. aureus in agar test plates, as millimeters of zone of inhibition. The tests were carried out in triplicate as follows:

Bacteriological tests were performed against Staphylococcus aureus with a 24-hour culture at 37 C. Each of the compounds in Table I was incorporated in soap of ivory brand (a neutral white high grade toilet soap consisting of a mixture of 80% sodium soap and 20% potassium soap produced from a 70% tallow and 30% coconut oil glyceride blend, in accordance with US. Patent 2,295,594), in 1% by weight concentration of soap and 0.1% of the compound listed. Cotton disks of 10 mm. diameter were steeped in this mixture, thoroughly rinsed, dried, and applied to seeded agar in Petri dishes, and the zones of inhibition were read after 24 hours, the average data being reported in Table I.

These compounds of the present invention are useful in compositions comprising a germicidally inert material, i.e., relatively speaking. For example, some soaps and detergents possess a bactericidal action, but such action, relative to those of the compounds of the present invention, is weak and of little effect in comparison with the overall germicidal activity of the composition. In such compositions, the compounds of the present invention may be employed in concentrations as low as 10 p.p.m., although from a practical point of view, it is desirable to atent O 3,3 l L502 Patented Mar. 28, 1967 use as much as 50 p.p.m. or 0.001% by weight, or 0.01%, and as much as 0.1%, or more. The term germicidal activity includes inhibiting and killing action against bacteria, fungi and similar organisms.

Particularly useful compositions of the present invention are those comprising soaps and detergents, and especially toilet soaps or cosmetic detergents in which the compounds of the present invention may be employed in concentrations of 0.1% to 0.5% by weight, or even as much as 1% or more. The term detergent employed herein will be used to include all synthetic and natural cleansing compositions, including cationic detergents, such as dimethyl stearamido-propyl-Z hydroxy-ammonium dihydrogen phosphate, anionic detergents such as commercial soaps, e.g., alkali metal soaps of hydrolyzed natural or synthetic glycer-ides of fatty and similar organic acids, e.g., sodium and potassium stearates or oleates, ampholytic detergents, such as sarcosine, non-ionic deter-- gents such as polyoxypropylene polyoxyethylene condensates, natural detergents, such as starches, vegetable gums, and the like, and mixtures thereof. The term soap employed herein is used in its popular or ordinary meaning, i.e., a cleansing composition prepared from an alkali metal compound such as potassium or sodium hydroxide and a fat or fatty acid, both saturated and unsaturated.

One valuable use of the compounds of the present invention is the use thereof to sanitize fibrous material such as cotton gauze, dressings, textiles, paper pulp, and the like. They also serve as antiseptic agents when incorporated in plastic or rubber compositions, prior to molding into articles of commerce, such as baby rattles, gloves, food wrappers and the like.

Compound Zone of No. Formula Inhibition,

SH it 1 01 SH I I H I 2 l l H 3 CN Br 5.5

Br S F 1 fl 1? 4 SH it 5 l I Br SH I l 0 H H l 6 CN 01 2.5

Compound Zone of No. Formula Inhibition,

IIHH.

F sn rt-Q 7 or- O H 2.0

01 sn ts (31- g I 2.5

en rt- 01 9 S H SH rim g, N en iii" 12 H on Br or l filli 15 SH it 16 @oN B1 4.5

' it 11 CN 4.5

sn ii 18 From a study of Table I, it Will be observed that the germicidal potency of the compounds of the present invention do not appear to be increased substantially by the addition of halogen atoms to the nuclei. This is apparent by comparing Compound No. l with No. 2, for example, and Compound No. 9 with No. 10. However, the germicidal properties are appreciably greater with phenyl than with naphthyl nuclei, as may be seen through comparison of Compound No. l with No. 11. It is thus apparent that the exceptional germicidal potency of the compounds of the present invention is inherent mostly in the structural arrangement of the molecule, rather than to the halogen substituents.

I claim:

1. A germicidal detergent composition consisting essentially of a detergent selected from the group consisting of anionic, cationic, non-ionic, and ampholytic, and about 0.01% to about 1.0%, by weight, of a sulfur-containing compoundhaving the general formula:

3. A germicidal detergent composition, according to claim 1, essentially of a detergent selected from the group consisting of anionic, cationic, non-ionic, and ampholytic, and about 0.01% to about 1.0%,- by Weight, of the compound:

oN- Br 4. A germicidal detergent composition, according to claim 1, consisting essentially of a detergent selected from the group consisting of anionic, cationic, non-ionic, and ampholytic, and about 0.01% to about 1.0%, by weight,

of the compound:

01 SH t 5. A germicidal detergent composition, according to claim 1, consisting essentially of a detergent selected from the group consisting of anionic, cationic, non-ionic, and ampholytic, and about 0.01% to about 1.0%, by weight, of the compound:

6. A germicidal detergent composition, according to claim 1, consisting essentially of a detergent selected from the group consisting of anionic, cationic, non-ionic, and

5 ampholytic, and about 0.01% to about 1.0%, by weight, OTHER REFERENCES of the compound: Hopper, I. V., et al.: The Preparation of Certain Thiolca-rboxylic Acids and Their Arylamides, J. Soc. Dyers Br SH F Colourists 57: 6-9 (1941), abstracted in Chem. Abstracts ff f 5 35: 2484 (8)-2484 (2) 1 941).

G Gialdi et 211.: Dialkylaminoalkyl N or S-derivatives of Br and 2-(arylthi0)-benzamides, Farmaco (Ravia), Ed, Sci.

16: 411-437 (1961); vabstracted in Chem. Abstracts 56: 10 4664g-4666g (1962).

LEON D. ROSDOL, Primary Examiner.

LEWIS GOTTS, Examiner. 3,041,236 6/ 1962 Stecker 252107 X S, K. ROSE, S. E. DARDEN, Assistant Examiners.

References Cited by the Examiner UNITED STATES PATENTS 

1. A GERMICIDAL DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A DETERGENT SELECTED FROM THE GROUP CONSISTING OF ANIONIC, CATIONIC, NON-IONIC, AND AMPHOLYTIC, AND ABOUT 0.01% TO ABOUT 1.0%, BY WEIGHT, OF A SULFUR-CONTAINING COMPOUND HAVING THE GENERAL FORMULA: 